On the decomposition of β phase in some rapidly quenched titanium-eutectoid alloys

The decomposition of the β phase in rapidly quenched Ti-2.8 at. pct Co, Ti-5.4 at. pct Ni, Ti-4.5 at. pct, and 5.5 at. pct Cu alloys has been investigated by electron microscopy. During rapid quenching, two compctitive phase transformations, namely martensitic and eutectoid transformation, have occurred, and the region of eutectoid transformation is extended due to the high cooling rates involved. The β phase decomposed into nonlamellar eutectoid product (bainite) having a globular morphology in Ti-2.8 pct Co and Ti-4.5 pct Cu (hypoeutectoid) alloys. In the near-eutectoid Ti-5.5 pct Cu alloy, the decomposition occurred by a lamellar (pearlite) type, whereas in Ti-5.4 pct Ni (hypereutectoid), both morphologies were observed. The interfaces between the proeutectoid α and the intermetallic compound in the nonlamellar type as well as between the proeutectoid α and the pearlite were often found to be partially coherent. These findings are in agreement with the Lee and Aaronson model proposed recently for the evolution of bainite and pearlite structures during the solid-state transformations of some titanium-eutectoid alloys. The evolution of the Ti₂Cu phase during rapid quenching involved the formation of a metastable phase closely related to an “ω-type” phase before the equilibrium phase formed. Further, the lamellar intermetallic compound Ti₂Cu was found to evolve by a sympathetic nucleation process. Evidence is established for the sympathetic nucleation of the proeutectoid a crystals formed during rapid quenching.     

Decomposition of Fe-Ni martensite: Implications for the low-temperature (≤500 °C) Fe-Ni phase diagram

The low-temperature (<500 °C) decomposition of Fe-Ni martensite was studied by aging martensitic Fe-Ni alloys at temperatures between 300 °C and 450 °C and by measuring the composition of the matrix and precipitate phases using the analytical electron microscope (AEM). For aging treatments between 300 °C and 450 °C, lath martensite in 15 and 25 wt pct Ni alloys decomposed with γ [face-centered cubic (fcc)] precipitates forming intergranularly, and plate martensite in 30 wt pct Ni alloys decomposed with γ (fcc) precipitates forming intragranularly. The habit plane for the intragranular precipitates is {111}_fcc parallel to one of the {110}_bcc planes in the martensite. The compositions of the γ intergranular and intragranular precipitates lie between 48 and 58 wt pct Ni and generally increase in Ni content with decreasing aging temperature. Diffusion gradients are observed in the matrix α [body-centered cubic (bcc)] with decreasing Ni contents close to the martensite grain boundaries and matrix/precipitate boundaries. The Ni composition of the matrix α phase in decomposed martensite is significantly higher than the equilibrium value of 4 to 5 wt pct Ni, suggesting that precipitate growth in Fe-Ni martensite is partially interface reaction controlled at low temperatures (<500 °C). The results of the experimental studies modify the γ/α + γ phase boundary in the present low-temperature Fe-Ni phase diagram and establish the eutectoid reaction in the temperature range between 400 °C and 450 °C. Formerly Research Assistant, Department of Materials Science and Engineering, Lehigh University     

Transformations in α 2+γ titanium aluminide alloys containing molybdenum: Part II. Heat treatment

The response of as-cast structures of 12 alloys in the Ti-Al-Mo system containing 44 to 50 at. pct Al and 2 to 6 at. pct Mo to simple single step heat treatments in the temperature range 1373 to 1673 K is described. The microsegregation patterns present in the cast structure persist to a large extent after heat treatment, especially below 1673 K. However, tentative conclusions regarding phase equilibria in this temperature and composition range are drawn from the results. High-temperature equilibria are dominated by the β, α+β, and α+γ phase fields, while the β+γ phase field dominates equilibrium below 1473 K. Three major types of transformation behavior are observed: a massive α to γ transformation, which occurs within the α phase on quenching from 1673 and 1573 K in alloys centered around the 48 pct Al composition; a eutectoid transformation from α to B2+γ mixtures, which occurs at 1473 K and below in alloys centered around the 48Al-4Mo and 46Al-6Mo compositions; direct γ precipitation in β, which occurs primarily in the 44Al-6Mo composition at 1273 K and below; and finally growth of γ lamellae in α+γ lamellar structures with B2 precipitation on lamellar interfaces, which occurs over a broad range of alloy compositions and temperatures.     

Constitution of the Ni-Cr-Fe system from 0 to 40 pct fe including some effects of Ti,Al, Si,and Nb

The positions of the γ/γ + α′ solvus for nickel-rich Ni-Cr-Fe alloys containing 0 to 40 pct Fe have been determined from 816° to 1260°C (1500° to 2300°F) to within 2 wt pct Cr. In addition, the individual effects of Ti, Al, Si, and Nb on the position of the γ/γ + α′ solvus have been determined.     

Determination of the Fe-Ni and Fe-Ni-P phase diagrams at low temperatures (700 to 300 °C)

The α + γ two-phase fields of the Fe-Ni and Fe-Ni (P saturated) phase diagrams have been determined in the composition range 0 to 60 wt pet Ni and in the temperature range 700 to 300 °C. The solubility of Ni in (FeNi)₃P was measured in the same temperature range. Homogeneous alloys were austenitized and quenched to form α₂, martensite, then heat treated to formα (ferrite) + γ (austenite). The compositions of the α and γ phases were determined with electron microprobe and scanning transmission electron microscope techniques. Retrograde solubility for the α/(α + γ) solvus line was demonstrated exper-imentally. P was shown to significantly decrease the size of the α + γ two-phase field. The maximum solubility of Ni in α is 6.1 ± 0.5 wt pct at 475 °C and 7.8± 0.5 wt pct at 450 °C in the Fe-Ni and Fe-Ni (P saturated) phase diagrams, respectively. The solubility of Ni in α is 4.2 ± 0.5 wt pct Ni and 4.9 ± 0.5 wt pct Ni at 300 °C in the Fe-Ni and Fe-Ni (P saturated) phase diagrams. Ternary Fe-Ni-P isothermal sections were constructed between 700 and 300 °C. Formerly Research Assistant in Department of Metallurgy & Materials Engineering, Lehigh University, Bethlehem, PA.     

The microstructure of rapidly solidified Ti-Fe melt-spun ribbons

Ti-Fe binary alloys were rapidly solidified by the melt-spinning technique, and four compositions were examined: Ti-5 wt pct Fe, which is the critical composition for theβ to ω athermal transformation; Ti-10 wt pct Fe, which represents a hypoeutectoid composition; the eutectoid composition Ti-15 wt pct Fe; and Ti-20 wt pct Fe, as an example of a hypereutectoid alloy. The Ti-5 wt pct Fe rapidly solidified ribbons are composed of two different structures. The first consists of α′-martensite plates inβ matrix and the second, athermal ω particles inβ matrix. The Ti-10, 15, and 20 wt pct Fe alloys are also composed of two structures. These areβ grains and isothermal-like ω particles inβ matrix. A solidification model is suggested which explains the existence of two different microstructures at the same composition and the for-mation of two kinds of ω particles.     

The morphology,crystallography, and chemistry of phases in as-cast nickel-aluminum bronze

The morphology, crystallography, and composition of the phases present in as-cast nickel-aluminum bronze of nominal composition copper-10 wt pct aluminum-5 wt pct nickel-5 wt pct iron have been investigated using optical, electron optical, and microprobe analysis techniques. The as-cast microstructure consists of copper-rich α, martensitic β, and κ-phases based on Fe₃Al and NiAl. The κ_z precipitates have a dendritic morphology and are cored; the composition ranges from iron-rich solid solution to Fe₃Al. The κ_II and κ_iv precipitates have, respectively, a dendritic and an equiaxed/dendritic morphology, and are based on Fe₃Al, while κ_III is a eutectoidal decomposition product of lamellar or globular morphology based on NiAl. The κ_I, κ_II, and κ_III precipitates have the Kurdjumov-Sachs orientation relationship with α matrix. Small κ_IV precipitates exhibit the Nishiyama-Wasserman orientation relationship with the α matrix, while large κ_iv precipitates have an orientation relationship which lies between Kurdjumov-Sachs and Nishiyama-Wasserman.     

Microstructure and phase identification in type 304 stainless steel-zirconium alloys

Stainless steel-zirconium alloys have been developed at Argonne National Laboratory to contain radioactive metal isotopes isolated from spent nuclear fuel. This article discusses the various phases that are formed in as-cast alloys of type 304 stainless steel and zirconium that contain up to 92 wt pct Zr. Microstructural characterization was performed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), and crystal structure information was obtained by X-ray diffraction. Type 304SS-Zr alloys with 5 and 10 wt pct Zr have a three-phase microstructure—austenite, ferrite, and the Laves intermetallic, Zr(Fe,Cr,Ni)_2+x. whereas alloys with 15, 20, and 30 wt pct Zr contain only two phases—ferrite and Zr(Fe,Cr,Ni)_2+x. Alloys with 45 to 67 wt pct Zr contain a mixture of Zr(Fe,Cr,Ni)_2+x and Zr₂(Ni,Fe), whereas alloys with 83 and 92 wt pct Zr contain three phases—α-Zr, Zr₂(Ni,Fe), and Zr(Fe,Cr,Ni)_2+x. Fe₃Zr-type and Zr₃Fe-type phases were not observed in the type 304SS-Zr alloys. The changes in alloy microstructure with zirconium content have been correlated to the Fe-Zr binary phase diagram.     

Effects of carbon content and ausaging on γ ↔ α′ transformation behavior and reverse-transformed structure in Fe-Ni-Co-Al-C alloys

The effects of carbon content and ausaging on austenite γ ↔ martensite (α′) transformation behavior and reverse-transformed structure were investigated in Fe-32Ni-12Co-4Al and Fe-(26,28)Ni-12Co-4Al-0.4C (wt pct) alloys. TheM _s temperature, the hardness of γ phase, and the tetragonality of α′ increase with increasing ausaging time, and these values are higher in the carbon-bearing alloys in most cases. The γ → α′ transformation behavior is similar to that of thermoelastic martensite; that is, the width of α′ plate increases with decreasing temperature in all alloys. The αt’ → γ reverse transformation temperature is lower in the carbon-bearing alloys, which means that the shape memory effect is improved by the addition of carbon. The maximum shape recovery of 84 pct is obtained in Fe-28Ni-12Co-4Al-0.4C alloy when the ausaged specimen is deformed at theM _s temperature and heated to 1120 K. There are two types of reverse-transformed austenites in the carbon-bearing alloy. One type is the reversed y containing many dislocations which were formed when the γ/α′ interface moved reversibly. The plane on which dislocations lie is (01 l)_γ if the twin plane is (112)_α′. The other type of reverse-transformed austenite exhibits γ islands nucleated within the α′ plates.     

Deformation and fracture behavior of a directionally solidified β/γ′ Ni-30 At. pct Al alloy

The effect of a ductile γ′-Ni₃Al phase on the room-temperature ductility, temperature-dependent yield strength, and creep resistance of β-NiAl was investigated. Room-temperature tensile ductility of up to 9 pct was observed in directionally solidified β/γ′ Ni-30 at. pct Al alloys, whereas the ductility of directionally solidified (DS), single-phase [001] β-NiAl was negligible. The enhancement in ductility was attributed to a combination of slip transfer from the ductile γ′ to the brittle β phase and extrinsic toughening mechanisms such as crack blunting, deflection, and bridging. As in single-phase Ni₃Al, the temperature-dependent yield strength of these two-phase alloys increased with temperature with a peak at approximately 850 K. The creep strength of the β/γ′ alloys in the temperature range 1000 to 1200 K was found to be comparable to that of monolithic β-NiAl. A creep strengthening phase needs to be incorporated in the β/γ′ microstructure to enhance the elevated temperature mechanical properties.     

Influence of Al and Ni concentration on the Martensitic transformation in Cu-Al-Ni shape-memory alloys

The martensitic transformation temperatures and the types of martensitic phases have been determined in a wide concentration range of technological interest for Cu-Al-Ni shape-memory alloys (SMAs) A stability diagram of martensitic phases as a function of alloy concentration has been determined. It is found that when the aluminum content increases, the transformation changes from β ₃ ⇒ β′₃ to β ₃ ⇒ γ′₃, with an intermediate concentration range where both martensites coexist due to a β ₃ ⇒ γ′₃+β′₃ transformation. On the other hand, an increase of nickel content stabilizes the martensite β′₃, changing from a mixed β ₃ ⇒ γ′₃ + β′₃ to a single β ₃ ⇒ β′₃ transformation. Furthermore, linear relationships between M _s and Al and Ni concentrations have been obtained for all types of martensitic phases.     

The effect of molybdenum on γ′ coarsening and on elevated-temperature hardness in some experimental nickel-base superalloys

The coarsening of γ′ and the elevated-temperature hardness have been studied as a function of molybdenum content, time, and temperature in experimental wrought nickel-base superalloys. The alloys were selected from a systematic series containing 3, 4 1/2, and 6 wt pct Al and 1 wt pct Al plus 3 1/2 wt pct Ti. Each of the aluminum (plus titanium) series consisted of four alloys containing 0, 2, 5, and 8 wt pct Mo. The alloys were solution-treated plus aged up to 112 h at 1700°F (925°C) and up to 1000 h at 1400°F (760°C). Molybdenum retards the coarsening of γ′ on aging; this retarding effect is most pronounced in alloys containing 6 wt pct Al. The coarsening of γ′ particles follows Ostwald ripening kinetics. Hardness testingin vacuo at temperatures up to 1750°F (955°C) shows that molybdenum also increases the elevated-temperature hardness significantly. The relation of elevated-temperature hardness to the volume fraction of γ′ is considered, and the influence of aluminum and titanium contents is discussed.     

Evolution of boride morphologies in TiAl-B alloys

The solidification of γ-TiAl alloys with relatively low (<2 at. pct) additions of boron is discussed. Binary Ti-Al alloys containing 49 to 52 at. pct Al form primary α-(Ti) dendrites from the melt, which are subsequently surrounded by γ segregate as the system goes through the peritectic reactionL + α →γ. Alloys between 45 and 49 at. pct Al go through a double peritectic cascade, forming primary β-(Ti) surrounded by α-(Ti) and eventually by γ in the interdendritic spaces. Boron additions to these binary alloys do not change the basic solidifi-cation sequence of the matrix but introduce the refractory compound TiB₂ in a variety of mor-phologies. The boride develops as highly convoluted flakes in the leaner alloys, but needles, plates, and equiaxed particles gradually appear as the B content increases above ∼1 at. pct. Increasing the solidification rate initially promotes the formation of flakes over plates/needles and ultimately gives way to very fine equiaxed TiB₂ particles in the interdendritic spaces of the metallic matrix. Furthermore, the primary phase selection in the 49 to 52 at. pct Al range changes from α-(Ti) to β-(Ti) at supercoolings of the order of 200 K. The different boride morphologies are fully characterized, and their evolution is rationalized in terms of differences in their nucleation and growth behavior and their relationship to the solidification of the inter-metallic matrix. Formerly Research Assistant, University of California-Santa Barbara (UCSB) Formerly Professor of Materials and Dean of the College of Engineering at UCSB     

The effect of additives on the eutectoid transformation of ductile iron

The eutectoid transformation of austenite in cast iron is known to proceed by both the meta-stable γ → α + Fe₃C reaction common in Fe-C alloys of near eutectoid composition, and by the direct γ → α + Graphite reaction, with the graphite phase functioning as a car-bon sink. In addition, the meta-stable cementite constituent of the pearlite can dissolve near the graphite phase (Fe₃C → α + Graphite), producing free ferrite. Isothermal trans-formation studies on a typical ductile iron (nodular cast iron) confirmed that all of these reaction mechanisms are normally operative. The addition of 1.3 pct Mn was found to substantially retard all stages of the transformation by retarding the onset of the eutectoid transformation, decreasing the diffusivity of carbon in ferrite, and stabilizing the cemen-tite. Minor additions of Sb (0.08 pct) or Sn (0.12 pct) were found to inhibit the γ →α + Graphite reaction path, as well as the Fe₃C → α + Graphite dissolution step, but did not significantly affect the meta-stable γ → α + Fe₃C reaction. Scanning Auger microprobe analysis indicated that Sn and Sb adsorb at the nodule/metal interphase boundaries during solidification. This adsorbed layer acts as a barrier to the carbon flow necessary for the direct γ → α + Graphite and Fe₃C → α + Graphite reactions. With the graphite phase dis-abled as a sink for the excess carbon, the metal transforms like a nongraphitic steel. The effects of Mn, Sn, and Sb on the eutectoid transformation of ductile iron were shown to be consistent with their behavior in malleable iron.     

Interdiffusion in Ni-Rich,Ni-Cr-Al alloys at 1100 and 1200 °C: Part I. Diffusion paths and microstructures

Interdiffusion in Ni-rich, Ni-Cr-Al diffusion couples was studied after annealing at 1100 and 1200 °C. Recession of γ′ (Ni₃Al structure), β (NiAl structure), or α (bcc) phases was also measured. Aluminum and chromium concentration profiles were measured in the γ (fcc) phase for most of the diffusion couples. The amount and location of Kirkendall porosity suggests that Al diffuses more rapidly than Cr which diffuses more rapidly than Ni in the γ phase of Ni-Cr-Al alloys. The location of maxima and minima in the concentration profiles of several of the diffusion couples indicates that both cross-term diffusion coefficients for Cr and Al are positive and that D_CrAl has a greater effect on the diffusion of Cr than does D_A1Cr on the diffusion of Al. The γ/γ + β phase boundary has also been determined for 1200 °C through the use of numerous γ/γ+ β diffusion couples.     

Effect of phase morphology on the mechanical behavior of two titanium aluminide composites

Two binary titanium aluminide alloys, Ti-43A1 and Ti-47A1 (atomic percent), were discontinuously reinforced with 6 vol pct titanium diboride, resulting in a two-phase Ti₃Al and TiAl (α₂ and γ, respectively) matrix with a dispersion of TiB₂ particulate. Cast material was successfully ex-truded and subjected to a series of single-step and duplex-step heat treatments. Thermo-mechanical processing was correlated with microstructural changes, and the ambient temperature mechanical properties were measured for the various heat-treated conditions using tensile and hardness testing. Yield stress and plastic elongation to failure and hardness were found to cor-relate well with the fraction of proeutectoid, or primary, TiAl formed during heat treatment within the α/γ phase field. Precipitation of y within proeutectoid α grains during subsequent aging treatments within the α₂ phase field was seen to increase the room-temperature ductility with negligible debits in yield stress. Enhanced ductility and decreases in yield stress and hard-ness are associated with morphologically large regions of the TiAl phase. Incompatibility of slip systems across γ/α₂ and the inherent resistance to slip in hyperstoichiometric Ti₃Al are suggested as possible explanations for the observed phenomena. Formerly with Martin Marietta Laboratories     

The tempering of FeNiN martensite

The tempering behavior of ternary iron-nickel-nitrogen martensitic specimens (∼13.5 at. pct Ni, ∼4.7 at. pct N; ∼4.9 N atoms/100 metal atoms) in the temperature range of 270 to 670 K was investigated by analysis of the corresponding changes in the crystalline structure (X-ray diffraction), volume (dilatometry), and enthalpy (calorimetry). At least three stages of structural change can be distinguished: (1) redistribution of nitrogen atoms, involving segregation and formation of nitrogen enrichments, occurs at temperatures up to 370 K, (2) precipitation of γ′-(Fe, Ni)₄N_1-x nitride takes place in the temperature range of 370 to 430 K, and (3) coarsening of the γ′ precipitates and decomposition of a part of the retained austenite occur at temperatures above 430 K. From a comparison with the tempering behavior of a binary iron-nitrogen martensitic alloy containing a similar amount of interstitials, it was concluded that the presence of nickel suppresses the development of the intermediate α″-(Fe,Ni)₁₆N₂ nitride and advances the precipitation of γ′ nitride.     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,     

The titanium-rich end of the Ti-Cd phase diagram

Ti-Cd alloys containing up to 30 at. pct Cd have been prepared by diffusing cadmium from the vapor phase into pure titanium. Phase relations in these alloys have been explored by metallographic and X-ray techniques. Cadmium has quite a large solubility in theβ phase of titanium at 1000°C. Addition of cadmium decreases theα-β transformation temperature, forming a eutectoid at approximately 785°C. The solubility of cadmium inα titanium at the eutectoid temperature is approximately 6.5 at. pct, decreasing with decreasing temperature. The phase in equilibrium with saturatedα titanium is an intermetallic compound based on the composition Ti₂Cd.     

Electron microscopic determination of orientation

The martensites of titanium binary alloys, containing 1, 2, and 5.3 wt pct Cu, were studied by transmission electron microscopy techniques. Roughly parallel plates with different variants of the orientation relationship, as well as colonies of identical variant plates, prevail in the structures. A stereographic projection analysis of super-imposed diffraction patterns from two adjacent plates is shown to be sufficient for the deduction of the orientation relationship that existed during transformation, which is found to be the Burgers’ relationship -(110)_β∥ (0001)_α′; 〈111〉_β∥ 〈2110〉_α′. A graphical method was developed for the derivation of the habit plane and its particular variant, in spite of the absence of retained β phase in quenched Ti-Cu alloys. The habit plane of Ti-Cu martensite is found to be (1079)_β with 4 deg accuracy, and to best agree with Class A (α^- ω⁺) solution of the Bowles and Mackenzie theory, rather than with (α⁺ ω⁺) or with Class B solutions.